New organotin derivatives



United grates harem @fiice 3,019,247 Patented Jan. 30, 1962 The invention relates to new organotin derivatives, and this application is a continuationin-part of our copending application Serial No. 448,760, filed August 9, 1954, and issued as US. Patent No. 2,938,013 on May 24, 1960.

The novel compounds comprise reaction products of a partial ester of a dicarboxylic or polycarboxylic acid, which contain one free carboxyl group and at least one free alcoholic hydroxyl group, with an organotin compound selected from the group consisting of monomeric or polymeric organotin hydroxides, oxides, and flllCOXldGS. In said compounds, said ester is bound through the oxygen of the carboxyl group to the tin atom of the organo-tin compound and the free hydroxyl group of the ester component imparts to the compounds particularly valuable properties for the use as stabilizers for halogen-containing resins.

The compounds may be broadly defined by the general formula 1 R R XSnZ wherein R and R represent different or preferably the same aliphatic, alicyclic, or aromatic hydrocarbon radicals; Z is the radical of an ester of a polycarboxylic acid in which all but one of the carboxyl groups are esterified by a dihydric or polyhydric alcohol. In the simplest case, Z is the radical of a half ester of a dicarboxylic acid of the formula (2) OOCR COOY wherein R is a saturated or unsaturated divalent hydrocarbon radical and Y the residue of a dihydric or polyhydric alcohol containing at least one free hydroxyl group. X is a member of the group consisting of R 0R Z and (R R SnO) Z, wherein the last recited group is characteristic for polymeric compounds of the type involved. R designates the same type of hydrocarbon radical as represented by R and R if X is R the compounds are esters of trihydrocarbontin hydroxides; OR is an allroxy radical derived from aliphatic, alicyclic, or aromatic alcohols, and the compounds containing 0R are ether esters of hydrocarbon substituted stannanediols, Whereas in the case of X=Z the compounds are diesters of such stannanediols. If X is the group (R R SnO) Z, the compounds are esters of linear hydrocarbon substituted polys-tannanediols, where x designates the degree of polymerization.

The ester used for introducing the group Z may be composed of any combination of a diand polycarboxylic acid with a glycol or polyol. Suitable acids are, for in stance, adipic acid, sebacic acid, fumaric acid, maleic acid, succinic acid, malonic acid, glutaric acid, itaconic acid, aconitic acid, citraconic acid, citric acid, tartaric acid, and the like. As examples of suitable glycols and polyhydric alcohols, we may list: ethylene glycol, diethylene glycol, polyethylene glycol, the corresponding propylene glycols, glycerol, trimethylol methane, trimethylol propane, pentaerythritol, sorbitol and other sugar alcohols, and the like.

The new compounds are prepared by reacting an ester as defined hereinabove with an organotin axide, hydroxide or alkoxide; suitable organic groups of the organotin radical are, for instance, methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, lauryl, allyl, benzyl, phenyl, tolyl, furfuryl, cyclohexyl, naphthyl, and others. If the reaction is carried out with an organotin alkoxide, we prefer to use such an alkoxide which is derived from a lower alcohol, preferably a methoxide. If a monomeric dihydrocarbon tin dialkoxide is reacted with only one mole of the ester, the corresponding ether ester is obtained, i.e. a compound of the Formula 1, wherein X is alkoxide; with two moles of the ester, the diester is obtained-that is X=Z. In the case of polymeric dihydrocarbon tin dialkox-ides, polystannanediol derivatives of the formulae respectively, are obtained.

The compounds of the invention are mostly liquids when in the monomeric state; the higher polymers are colorless solids.

Like other organotin esters and ether esters, the new compounds are excellent stabilizers to protect halogencontaining resins against deterioration and discoloration due to the influence of heat and light. They are superior to said known esters and ether esters because the free hydroxyl groups of the ester component increases the compatibility of the new compounds with said resins and the plasticizers used therein.

Due to the highly polar nature of the novel ester compounds, their compatibility with resins and plasticizers is greatly enhanced; if decomposition should take place during heat processing, the decomposition products remain compatible with the resin and do not have the tendency of sweating out. Their properties are of particular importance in the preparation of optically clear rigid vinyl sheeting, where no polar plasticizers are present and incompatible ingredients would produce haziness and cloth. mg.

The most unexpected and valuable property of the new compounds, when compared with the corresponding organotin esters not containing free hydroxyl groups, is

- their insolubility or very much reduced solubility in fats.

This property makes the new compounds excellent stabilizers in wrappings and containers made of halogencontaining plastics whenever such containers are to be used for fats and fat containing foods.

The invention is further illustrated by the following examples, in which the amounts are given in parts by Weight.

Example 1 HO O O O OHzOHOHCHa HO O O 0 04139 s'n hon having the following characteristics Ref. ind. at 20 C.: 1.5060

Sp. gr. at 20 C.: 1.374

Sn found 19.5% (theory: 20.5%)

0 O C ("3H CHaOHOHCI-IzO O C CH 3 It is possible that the compond is a mixture of the two the precipitated sodium chloride and the toluene was disisomeric configurations of the maleic ester group tilled off.

CHCOOH 150 parts of the thus obtained polymeric dibutyltin I] dimethoxide having a polymerization degree of 1.3 were CHCOOCHZCHOHCH 5 dissolved in toluene, and 180 parts of dipropylene glycol or maleate half-ester were added to the solution. The meth- CHCOOH anol split off during the reaction was distilled out under CHOOOHCCH3 reduced pressure, together with the toluene. Theproduct CHZOH thus obtained had the formula In the same manner, the dibutyltin di(propylene glycol OtHr 04m ll HCCOOY C4119 OAHQ YOOCOH fumar-ate) was prepared.

Example 2 wherein '=HO CH'ZOHZC GI-IOHCHa What we claim is: 1. As a new chemical compound, dialkyl tin di(al- H2O=C "00 Sin 00o C=oru omooomoorrorromou otHl Example 3 kyleneglycol maleate) of the formula 61.4 parts of tributyltin hydroxide were slowly added R2Sn OOC("3H with stirring to 56 parts of di(ethyleneglycol) citrate in A1kQQCH ivl i ggzgi nil igggilg wgggppiig agd gl f iii i g si wherein R is alkyl and Alkisthe radical of a glycol seaction was rmoved ogether w h t Solvant The Ob lected from the group conslstrng of monoethyleneglycol, M dlethyleneglycol, monopropyleneglycol and dipropylenetamed compound had the formula glycol and containing one free alcoholic hydroxyl group. 2. As a new compound, dibutyltin di(propyleneglycol (H1003 Sn 000C111 maleate) of the formula HOHzCCHzOOCCOH IICIJCOOCH2CHOHCHS nn, 'nonzoomoocoln H0000 Sin OOC'CH c in cuacnoncr-rzooccn S-n found 21.0% (theory 21 .4%).

. 40 References Cited 1n the file of this patent Example 4 UNITED STATES PATENTS Polymeric dibutyltin dimethoxide was prepared ord- 1,917,249 Harris July 11, 1933 ing to Example 1 of Patent-No. 2,626,953, by gradually 2,531,990 Mack et 1 17, 1953 adding at a temperature ofO" C; sodium methoxide to di- 2,71 5 111 Weinberg Aug 9, 1955 butyl tin chloride dissolved in toluene. Af r sh r h 2,796,412 Weinberg June 18, 1957 ing to C., the reaction product was filtered hot from 2 832,752 Weinberg et a1 Apr. 29, 1958 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,019,247 January .30 1962 Gerry P. Mack et all It is hereby certified that error appears in the above numbered pat- 'ent requiring correction and that the said Letters Patent should read as corrected below.

Column 4, lines 26 to 29, the formula shoul shown below lnstead of as in the patent:

sn -oocfis AlkOOCCH 2 Signed and sealed this 15th day of October 1963.

d appear as (SEAL) Attest:

EDWIN L.a REYNOLDS ERNEST W. SWIDER Attesting Officer AC g Commissioner of Patents 

1. AS A NEW CHEMICAL COMPOUND, DIALKYL TIN DI(ALKYLENEGLYCOL MALEATE) OF THE FROMULA 